CN113831324A - Compound and preparation method and application thereof - Google Patents
Compound and preparation method and application thereof Download PDFInfo
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- CN113831324A CN113831324A CN202111286037.1A CN202111286037A CN113831324A CN 113831324 A CN113831324 A CN 113831324A CN 202111286037 A CN202111286037 A CN 202111286037A CN 113831324 A CN113831324 A CN 113831324A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 102
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000010410 layer Substances 0.000 claims description 109
- 239000001257 hydrogen Substances 0.000 claims description 90
- 229910052739 hydrogen Inorganic materials 0.000 claims description 90
- 150000002431 hydrogen Chemical class 0.000 claims description 58
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 44
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 32
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 32
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 28
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 28
- 238000002347 injection Methods 0.000 claims description 24
- 239000007924 injection Substances 0.000 claims description 24
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 22
- 239000002356 single layer Substances 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 239000012752 auxiliary agent Substances 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 14
- 230000005525 hole transport Effects 0.000 claims description 14
- -1 borate ester Chemical class 0.000 claims description 13
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 12
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical group [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052794 bromium Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 7
- 125000006274 (C1-C3)alkoxy group Chemical group 0.000 claims description 6
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 6
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 6
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical group [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 5
- 125000001246 bromo group Chemical group Br* 0.000 claims description 5
- 239000011630 iodine Chemical group 0.000 claims description 5
- 229910052740 iodine Chemical group 0.000 claims description 5
- 235000011056 potassium acetate Nutrition 0.000 claims description 5
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical group [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical group C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- NXQGGXCHGDYOHB-UHFFFAOYSA-L cyclopenta-1,4-dien-1-yl(diphenyl)phosphane;dichloropalladium;iron(2+) Chemical group [Fe+2].Cl[Pd]Cl.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 NXQGGXCHGDYOHB-UHFFFAOYSA-L 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims description 3
- SGCLBIRCSTXTIU-UHFFFAOYSA-N boric acid;2,3-dimethylbutane-2,3-diol Chemical group OB(O)O.CC(C)(O)C(C)(C)O.CC(C)(O)C(C)(C)O SGCLBIRCSTXTIU-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 10
- 230000003111 delayed effect Effects 0.000 abstract description 6
- 230000005284 excitation Effects 0.000 abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 27
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 16
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 16
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 16
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 15
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 7
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000012300 argon atmosphere Substances 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000003480 eluent Substances 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical class [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- SSXSFTBOKUQUAX-UHFFFAOYSA-N (4-bromophenyl)-(4-fluorophenyl)methanone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=C(Br)C=C1 SSXSFTBOKUQUAX-UHFFFAOYSA-N 0.000 description 3
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- JSEQNGYLWKBMJI-UHFFFAOYSA-N 9,9-dimethyl-10h-acridine Chemical compound C1=CC=C2C(C)(C)C3=CC=CC=C3NC2=C1 JSEQNGYLWKBMJI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- UWCZIRUJFYRXKE-UHFFFAOYSA-N 1,5-dimethylacridine Chemical group C1=CC=C2C=C3C(C)=CC=CC3=NC2=C1C UWCZIRUJFYRXKE-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- GEQBRULPNIVQPP-UHFFFAOYSA-N 2-[3,5-bis(1-phenylbenzimidazol-2-yl)phenyl]-1-phenylbenzimidazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2N=C1C1=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=C1 GEQBRULPNIVQPP-UHFFFAOYSA-N 0.000 description 1
- DENKGPBHLYFNGK-UHFFFAOYSA-N 4-bromobenzoyl chloride Chemical compound ClC(=O)C1=CC=C(Br)C=C1 DENKGPBHLYFNGK-UHFFFAOYSA-N 0.000 description 1
- MZYDBGLUVPLRKR-UHFFFAOYSA-N 9-(3-carbazol-9-ylphenyl)carbazole Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC(N2C3=CC=CC=C3C3=CC=CC=C32)=CC=C1 MZYDBGLUVPLRKR-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- AVTASQJTDUCKMG-UHFFFAOYSA-L disodium;sulfate;pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O AVTASQJTDUCKMG-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001506 fluorescence spectroscopy Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001269 time-of-flight mass spectrometry Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000003949 trap density measurement Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention discloses a compound and a preparation method and application thereof. The compound can be used as a thermal excitation delayed fluorescence material for preparing an organic electroluminescent device.
Description
Technical Field
The invention relates to a compound, a preparation method and application thereof, in particular to a compound with thermal excitation delayed fluorescence property, a preparation method and application thereof.
Background
Compared with liquid crystal display technologies, Organic Light-Emitting Diodes (OLEDs) display technologies have the advantages of self-luminescence, wide viewing angle, low driving voltage, high contrast, fast response speed, and the like, and are gaining wide attention in academia and industry. In 2009, Adachi et al firstly apply a Thermal excited Delayed Fluorescence (TADF) material based on a triplet exciton intersystem crossing mechanism to an organic electroluminescent device, and successively obtain a metal-free TADF material and a green TADF material with IQE close to 100%, thereby realizing the design and synthesis of a metal-free high-efficiency luminescent material and the development of OLEDs. In addition, the TADF-based organic light-emitting material not only has a series of advantages of adjustable light-emitting color, wide raw material sources, simple synthesis process, etc., but also has light-emitting efficiency and device stability comparable to those of phosphorescent materials, and is called as a third-generation OLEDs light-emitting material.
CN106220649A discloses a diaryl ketone-based compound. The organic electroluminescent devices formed by the compounds still need a hole transport layer and an electron transport layer, the luminescent layer needs to be doped, and the current efficiency still needs to be improved.
CN106279203A discloses a compound containing ketone and nitrogen heterocycle. In the organic electroluminescent device formed using these compounds, a hole transport layer and an electron transport layer need to be present, and the light-emitting layer still needs to be doped.
CN107721981A discloses a compound containing 9, 9-dimethyl-9, 10-dihydroacridine. Organic light emitting devices formed using the compounds still require a hole transport layer and an electron transport layer, and current efficiency still remains to be improved. In addition, the multilayer doped device has a high turn-on voltage, which limits its widespread adoption.
CN108503603A discloses a polycyclic compound. Devices formed using the polycyclic compounds still require a hole transport layer and an electron transport layer, and current efficiency and turn-on voltage are to be improved.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a compound. The compound has thermal excitation delayed fluorescence performance, can be applied to organic electroluminescent devices including single-layer non-doped organic electroluminescent devices, and has high current efficiency and low starting voltage. Another object of the present invention is to provide a process for preparing the compound. The invention also aims to provide application of the compound in preparing an organic electroluminescent device, wherein the organic electroluminescent device can be a single-layer undoped organic electroluminescent device and can also be a multi-layer undoped organic electroluminescent device. The invention achieves the above object through the following technical scheme.
In one aspect, the present invention provides a compound having the structure of formula (I):
in the formula (I), R1、R2、R3、R4、R5、R6、R7And R8Represents a substituent at an arbitrary position on a benzene ring;
R1and R2Each independently selected from hydrogen, C1-C6 alkyl or C1-C6 alkoxy;
R3、R4、R5and R6Each independently selected from hydrogen, nitro, cyano or C1-C6 alkyl; r7And R8Each independently selected from hydrogen or C1-C6 alkyl.
According to the compounds of the invention, preferably:
R1and R2Each independently selected from hydrogen, C1-C3 alkyl or C1-C3 alkoxy;
R3、R4、R5and R6Each independently selected from hydrogen, nitro, cyano or C1-C3 alkyl; r7And R8Each independently selected from hydrogen or C1-C3 alkyl.
The compound according to the invention, preferably R1And R2Each independently selected from hydrogen, methyl, ethyl, methoxy or ethoxy.
The compound according to the invention, preferably R1And R2Are all hydrogen.
According to the compounds of the invention, preferably:
R3、R4、R5and R6Each independently selected from hydrogen, nitro or cyano;
R7and R8Each independently selected from hydrogen, methyl or ethyl.
The compound according to the present invention preferably has a structure represented by formula (II):
in another aspect, the present invention also provides a process for the preparation of a compound as described above, comprising the steps of:
(1) reacting a compound shown in a formula (A) with a compound shown in a formula (B) to obtain a first intermediate;
in the formula (A), R7And R8Each independently selected from hydrogen or C1-C6 alkyl; x is bromine or iodine; in the formula (B), R1And R2Each independently selected from hydrogen, C1-C6 alkyl or C1-C6 alkoxy;
(2) reacting the first intermediate with a borate ester to obtain a second intermediate;
(3) reacting the second intermediate with a compound shown as a formula (C) to obtain a compound shown as a formula (I);
in the formula (C), R3、R4、R5And R6Each independently selected from hydrogen, nitro, cyano or C1-C6 alkyl; y is selected from chlorine, bromine or iodine.
According to the preparation method of the present invention, preferably:
in the step (1), a compound shown as a formula (B) and a compound shown as a formula (A) in a molar ratio of 1.02-1.15: 1 are reacted under a first solvent and a first alkaline assistant to obtain a first intermediate;
in the step (2), reacting a first intermediate with borate in a molar ratio of 1: 1.5-4 in a second solvent, a first catalyst and a second basic auxiliary agent to obtain a second intermediate; wherein the borate is bis-pinacol borate;
in the step (3), the compound shown as the formula (C) with the molar ratio of 1.02-1.15: 1 and a second intermediate react under a third solvent, a second catalyst and a third alkaline assistant to obtain the compound shown as the formula (I).
According to the preparation method of the present invention, preferably:
in the step (1), the first solvent is N, N-dimethylformamide or N, N-dimethylacetamide, and the first alkaline auxiliary agent is potassium tert-butoxide;
in the step (2), the second solvent is 1, 4-dioxane, the first catalyst is [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride, and the second alkaline auxiliary agent is potassium acetate; the reaction temperature is 85-95 ℃, and the reaction time is 8-16 h;
in the step (3), the third solvent is toluene or ethylbenzene, and the second catalyst is tetrakis (triphenylphosphine) palladium; the third alkaline auxiliary agent is potassium carbonate; the reaction temperature is 80-90 ℃, and the reaction time is 8-16 h.
In still another aspect, the present invention also provides the use of the compound as described above in the preparation of an organic electroluminescent device, wherein the organic electroluminescent device is a single-layer undoped organic electroluminescent device or a multi-layer undoped organic electroluminescent device;
the single-layer undoped organic electroluminescent device comprises an anode layer, a hole injection layer, a light emitting layer, an electron injection layer and a cathode layer; wherein the light-emitting layer is formed of the compound as described above; the current efficiency of the single-layer non-doped organic electroluminescent device is greater than 10cd/A, and the starting voltage is lower than 2.8V;
the multilayer undoped organic electroluminescent device comprises an anode layer, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode layer; wherein the light-emitting layer is formed of the compound as described above; the current efficiency of the multilayer undoped organic electroluminescent device is larger than 39cd/A, and the starting voltage is lower than 2.7V.
The compound provided by the invention adopts a unit containing benzimidazole to modify a traditional TADF molecule, has definite TADF characteristics, has good carrier transmission property, can realize the balance of carrier injection, transmission and recombination, avoids the increase of exciton trap density under high current, can be used for forming a single-layer non-doped organic electroluminescent device, thereby omitting a hole transmission layer and an electron transmission layer, and the obtained single-layer non-doped organic electroluminescent device has high current efficiency and low starting voltage. In addition, the compound can be used for forming a multilayer undoped organic electroluminescent device, namely a hole transport layer and an electron transport layer are added into the device. In addition, only the compound of the present invention may be used as a light-emitting layer without doping other substances. The multilayer undoped organic electroluminescent device has higher current efficiency and lower starting voltage.
Detailed Description
The present invention will be further described with reference to the following specific examples, but the scope of the present invention is not limited thereto.
< Compound >
The compounds of the present invention are thermally-excited delayed fluorescence (TADF) molecules comprising a structure having an electron donor-acceptor (D-a). The structure of the compound of the invention is shown as the formula (I):
in the formula (I), R1、R2、R3、R4、R5、R6、R7And R8Represents a substituent at an arbitrary position on a benzene ring; i.e., a substituent at any position on the benzene ring. The compound can be used in OLEDs (including undoped OLEDs), and is beneficial to realizing carrier transport and recombination in a light-emitting layerThe balance of the combination is favorable for optimizing the luminous efficiency and stability of the device and keeping the lower starting voltage. In addition, the compound has bipolar transport characteristics, can replace the functions of the traditional electron and hole transport materials to a certain extent, and can be used for preparing monomolecular layer non-doped OLEDs. When the compound is applied to a device, good luminous efficiency can be achieved under the non-doping condition, and aggregation quenching behavior is limited. The compound has a structure of an electron transmission unit-electron acceptor unit (A) -electron donor unit (D), wherein the electron transmission unit is a benzimidazole-containing unit, the electron donor unit is a dimethylacridine-containing unit, and the electron acceptor unit is a benzophenone-containing unit. Whereas conventional TADF molecules generally adopt D-A or D-A-D type structures.
R1Selected from hydrogen, C1-C6 alkyl or C1-C6 alkoxy. Preferably, R1Selected from hydrogen, C1-C3 alkyl or C1-C3 alkoxy. More preferably, R1Selected from hydrogen, methyl, ethyl, methoxy or ethoxy. Examples of C1-C6 alkyl groups include, but are not limited to, methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl. Examples of C1-C6 alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, n-butoxy, isobutoxy, t-butoxy, n-pentoxy, n-hexoxy. According to one embodiment of the invention, R1Is hydrogen.
R2Selected from hydrogen, C1-C6 alkyl or C1-C6 alkoxy. Preferably, R2Selected from hydrogen, C1-C3 alkyl or C1-C3 alkoxy. More preferably, R2Selected from hydrogen, methyl, ethyl, methoxy or ethoxy. Examples of C1-C6 alkyl groups include, but are not limited to, methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl. Examples of C1-C6 alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, n-butoxy, isobutoxy, t-butoxy, n-pentoxy, n-hexoxy. According to one embodiment of the invention, R2Is hydrogen.
R3Selected from hydrogen, nitro, cyano or C1-C6 alkyl. Preferably, R3Selected from hydrogen, nitro, cyano or C1-C3 alkyl. More preferably, R3Selected from hydrogen, nitro or cyano. Examples of C1-C6 alkyl groups include, but are not limited to, methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl. According to one embodiment of the invention, R3Is hydrogen.
R4Selected from hydrogen, nitro, cyano or C1-C6 alkyl. Preferably, R4Selected from hydrogen, nitro, cyano or C1-C3 alkyl. More preferably, R4Selected from hydrogen, nitro or cyano. Examples of C1-C6 alkyl groups include, but are not limited to, methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl. According to one embodiment of the invention, R4Is hydrogen.
R5Selected from hydrogen, nitro, cyano or C1-C6 alkyl. Preferably, R5Selected from hydrogen, nitro, cyano or C1-C3 alkyl. More preferably, R5Selected from hydrogen, nitro or cyano. Examples of C1-C6 alkyl groups include, but are not limited to, methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl. According to one embodiment of the invention, R5Is hydrogen.
R6Selected from hydrogen, nitro, cyano or C1-C6 alkyl. Preferably, R6Selected from hydrogen, nitro, cyano or C1-C3 alkyl. More preferably, R6Selected from hydrogen, nitro or cyano. Examples of C1-C6 alkyl groups include, but are not limited to, methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl. According to one embodiment of the invention, R6Is hydrogen.
R7Selected from hydrogen or C1-C6 alkyl. Preferably, R7Selected from hydrogen or C1-C3 alkyl. More preferably, R7Selected from hydrogen, methyl or ethyl. Examples of C1-C6 alkyl groups include, but are not limited to, methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl. According to one embodiment of the invention, R7Is hydrogen.
R8Selected from hydrogen or C1-C6 alkyl. Preferably, R8Selected from hydrogen or C1-C3 alkyl. More preferably, R8Selected from hydrogen, methyl orAnd (4) ethyl. Examples of C1-C6 alkyl groups include, but are not limited to, methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl. According to one embodiment of the invention, R8Is hydrogen.
According to one embodiment of the invention, the compound has the structure shown in formula (II):
< preparation method >
The preparation method of the compound of the invention comprises the following steps: (1) synthesizing a first intermediate; (2) synthesizing a second intermediate; (3) synthesizing the target compound. As described in detail below.
Synthesis of the first intermediate
Reacting a compound represented by formula (A) with a compound represented by formula (B) to obtain a first intermediate. The structure of the first intermediate is shown as the following formula:
(first intermediate).
The specific choice of substituents for the first intermediate is the same as for formula (a) and formula (B).
The structure of the compound represented by the formula (A) is represented by the following formula:
in the formula (A), R7Selected from hydrogen or C1-C6 alkyl. Preferably, R7Selected from hydrogen or C1-C3 alkyl. More preferably, R7Selected from hydrogen, methyl or ethyl. Examples of C1-C6 alkyl groups include, but are not limited to, methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl. According to one embodiment of the invention, R7Is hydrogen.
In the formula (A), R8Selected from hydrogen or C1-C6 alkyl. Preferably, R8Selected from hydrogen or C1-C3 alkyl. More preferably, R8Selected from hydrogen, methyl or ethyl. Examples of C1-C6 alkyl groups include, but are not limited to, methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl. According to one embodiment of the invention, R8Is hydrogen.
In formula (A), X is bromine or iodine, preferably, X is bromine.
The structure of the compound represented by the formula (B) is represented by the following formula:
in the formula (B), R1Selected from hydrogen, C1-C6 alkyl or C1-C6 alkoxy. Preferably, R1Selected from hydrogen, C1-C3 alkyl or C1-C3 alkoxy. More preferably, R1Selected from hydrogen, methyl, ethyl, methoxy or ethoxy. Examples of C1-C6 alkyl groups include, but are not limited to, methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl. Examples of C1-C6 alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, n-butoxy, isobutoxy, t-butoxy, n-pentoxy, n-hexoxy. According to one embodiment of the invention, R1Is hydrogen.
In the formula (B), R2Selected from hydrogen, C1-C6 alkyl or C1-C6 alkoxy. Preferably, R2Selected from hydrogen, C1-C3 alkyl or C1-C3 alkoxy. More preferably, R2Selected from hydrogen, methyl, ethyl, methoxy or ethoxy. Examples of C1-C6 alkyl groups include, but are not limited to, methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl. Examples of C1-C6 alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, n-butoxy, isobutoxy, t-butoxy, n-pentoxy, n-hexoxy. According to one embodiment of the invention, R2Is hydrogen.
According to one embodiment of the invention, a compound represented by formula (B) and a compound represented by formula (a) in a molar ratio of 1.02 to 1.15:1 are reacted in a first solvent and a first basic auxiliary agent to obtain a first intermediate.
The molar ratio of the compound represented by the formula (B) to the compound represented by the formula (A) may be 1.02 to 1.15:1, preferably 1.05 to 1.15:1, and more preferably 1.08 to 1.1: 1.
The first solvent is N, N-dimethylformamide or N, N-dimethylacetamide, preferably N, N-dimethylformamide. The first alkaline auxiliary agent is potassium tert-butoxide. The molar ratio of the first basic auxiliary to the compound represented by the formula (a) may be 1.3 to 2:1, preferably 1.4 to 1.8:1, and more preferably 1.5 to 1.6: 1.
According to one embodiment of the invention, the compound shown in the formula (B) is dissolved in N, N-Dimethylformamide (DMF) and stirred at 0-10 ℃ under argon atmosphere; adding anhydrous potassium tert-butoxide into the system in batches, and continuously stirring for 4-8 h at 0-10 ℃. Slowly adding the compound shown in the formula (A) into the mixed system, naturally heating to room temperature, and continuously stirring for reacting for 8-16 h. Heating to 55-65 ℃, continuously stirring for reaction for 8-16 h, and cooling to room temperature. The reaction was poured into a dilute hydrochloric acid solution, washed three times with water, and then sufficiently extracted with dichloromethane. Drying the dichloromethane organic phase with sufficient anhydrous magnesium sulfate or sodium sulfate pentahydrate, filtering, vacuum concentrating, separating the concentrate by column chromatography, and eluting with a mixed solvent of petroleum ether and dichloromethane at a volume ratio of 5:1 to obtain a first intermediate.
The compound represented by the formula (a) can be prepared by the following reaction:
synthesis of the second intermediate
The first intermediate is reacted with a borate to provide a second intermediate. According to one embodiment of the invention, the borate ester is a bis-pinacol borate ester. The structural formula of the second intermediate is shown as follows:
(second intermediate).
According to one embodiment of the invention, a first intermediate and a borate ester are reacted in a molar ratio of 1: 1.5-4 in a second solvent, a first catalyst and a second basic auxiliary agent to obtain a second intermediate.
In the present invention, the molar ratio of the first intermediate to the borate ester may be 1:1.5 to 4, preferably 1:2 to 4, and more preferably 1:2.5 to 3.5. The reaction temperature may be 85 to 95 ℃, preferably 87 to 95 ℃, and more preferably 90 to 95 ℃. The reaction time may be 8 to 16 hours, preferably 10 to 14 hours, and more preferably 11 to 13 hours.
The second basic auxiliary agent is potassium acetate. The molar ratio of the first intermediate to the potassium acetate may be 1: 4-8, preferably 1: 5-7, and more preferably 1: 5.5-6.5.
The first catalyst may be [1,1' -bis (diphenylphosphino) ferrocene]Palladium dichloride (Pd (dppf) Cl2). The molar ratio of the first catalyst to the first intermediate may be 0.01 to 0.1:1, preferably 0.02 to 0.07:1, and more preferably 0.03 to 0.06: 1.
The second solvent may be 1, 4-dioxane. In the present invention, the amount of the second solvent may be 30 to 55mL based on 1g of the first intermediate.
Synthesis of the target Compound
And (3) reacting the second intermediate with the compound shown in the formula (C) to obtain the compound shown in the formula (I).
In the formula (C), R3Selected from hydrogen, nitro, cyano or C1-C6 alkyl. Preferably, R3Selected from hydrogen, nitro, cyano or C1-C3 alkyl. More preferably, R3Selected from hydrogen, nitro or cyano. Examples of C1-C6 alkyl groups include, but are not limited to, methyl, ethyl, propyl, n-butyl, isobutyl, t-butyl, n-pentylAnd hexyl. According to one embodiment of the invention, R3Is hydrogen.
In the formula (C), R4Selected from hydrogen, nitro, cyano or C1-C6 alkyl. Preferably, R4Selected from hydrogen, nitro, cyano or C1-C3 alkyl. More preferably, R4Selected from hydrogen, nitro or cyano. Examples of C1-C6 alkyl groups include, but are not limited to, methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl. According to one embodiment of the invention, R4Is hydrogen.
In the formula (C), R5Selected from hydrogen, nitro, cyano or C1-C6 alkyl. Preferably, R5Selected from hydrogen, nitro, cyano or C1-C3 alkyl. More preferably, R5Selected from hydrogen, nitro or cyano. Examples of C1-C6 alkyl groups include, but are not limited to, methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl. According to one embodiment of the invention, R5Is hydrogen.
In the formula (C), R6Selected from hydrogen, nitro, cyano or C1-C6 alkyl. Preferably, R6Selected from hydrogen, nitro, cyano or C1-C3 alkyl. More preferably, R6Selected from hydrogen, nitro or cyano. Examples of C1-C6 alkyl groups include, but are not limited to, methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl. According to one embodiment of the invention, R6Is hydrogen.
In the formula (C), Y is selected from chlorine, bromine or iodine. Preferably, Y is bromine.
According to one embodiment of the invention, the compound shown as the formula (C) with the molar ratio of 1.02-1.15: 1 and a second intermediate are reacted under the conditions of a third solvent, a second catalyst and a third basic auxiliary agent to obtain the compound.
The molar ratio of the compound represented by the formula (C) to the second intermediate may be 1.02 to 1.15:1, preferably 1.05 to 1.15:1, and more preferably 1.07 to 1.1: 1.
The second catalyst is tetrakis (triphenylphosphine) palladium (Pd (PPh)3)4). The molar ratio of the second catalyst to the second intermediate may be 0.02 to 0.1:1, preferably 0.03 to 0.06:1, more preferably 0.03-0.04: 1.
The third alkaline assistant is potassium carbonate. Potassium carbonate forms a saturated potassium carbonate solution when used. The weight of the second intermediate is 1g as a reference, and the using amount of the saturated potassium carbonate solution is 4.5-6 mL.
The third solvent is toluene or ethylbenzene, preferably toluene. The amount of the third solvent is 25 to 60mL, preferably 30 to 60mL, based on 1g of the second intermediate.
The reaction temperature may be 80 to 90 ℃, preferably 83 to 90 ℃, and more preferably 85 to 90 ℃. The reaction time may be 8-16 h, preferably 10-16 h, and more preferably 11-14 h.
According to one embodiment of the present invention, the compound of formula (C), the second intermediate and a catalytic amount of Pd (PPh)3)4Adding the mixture into a reaction bottle, adding toluene and a saturated potassium carbonate solution in an argon atmosphere, and stirring and reacting for 8-16 h at 80-90 ℃. After the reaction is finished, adding water to quench the reaction, extracting with ethyl acetate, taking an organic phase for concentration, carrying out column chromatography separation on the obtained concentrate by using a mixed solvent of ethyl acetate and n-hexane with the volume ratio of 1:10 as an eluent to obtain a solid, and then recrystallizing to obtain the target compound. The solvents used for recrystallization may be ethanol and toluene.
< application >
The invention also provides the application of the compound in preparing organic electroluminescent devices. The organic electroluminescent device may be a single-layer undoped organic electroluminescent device or a multi-layer undoped organic electroluminescent device.
The single-layer undoped organic electroluminescent device of the present invention includes an anode layer/a hole injection layer/a light emitting layer/an electron injection layer/a cathode layer. Preferably, the single-layer undoped organic electroluminescent device of the present invention is composed of an anode layer/a hole injection layer/a light emitting layer/an electron injection layer/a cathode layer. The light-emitting layer is formed from the compound described above. The current efficiency of the single-layer non-doped organic electroluminescent device is more than 10cd/A, preferably more than 10.05cd/A, and more preferably more than 10.1 cd/A. The turn-on voltage is less than 2.8V, preferably less than 2.75V, more preferably 2.7V or less.
According to one embodiment of the invention, the compound of the invention is used as a non-doped light-emitting layer, Indium Tin Oxide (ITO) and aluminum (Al) are used as an anode and a cathode, respectively, and molybdenum trioxide (MoO)3) And lithium fluoride (LiF) are respectively used as hole and electron injection materials, the substrate is glass, so that single-layer OLEDs without a transport layer are formed, the current efficiency of the device can reach 10.1cd/A, and the turn-on voltage is 2.7V. The maximum brightness of the device can reach 14600cd/m2。
The multilayer undoped organic electroluminescent device comprises an anode layer/a hole injection layer/a hole transport layer/a light emitting layer/an electron transport layer/an electron injection layer/a cathode layer. Preferably, the multilayer undoped organic electroluminescent device of the present invention is composed of an anode layer/a hole injection layer/a hole transport layer/a light emitting layer/an electron transport layer/an electron injection layer/a cathode layer. The light-emitting layer is formed from the compound described above. The current efficiency of the multilayer undoped organic electroluminescent device is more than 39cd/A, preferably more than 40cd/A, and more preferably more than 41 cd/A. The turn-on voltage is less than 2.7V, preferably less than 2.65V, more preferably 2.6V or less.
According to another embodiment of the present invention, a multi-layered undoped organic electroluminescent device comprises an ITO anode layer/hole injection layer (MoO)3) Hole transport layer (mCP)/light emitting layer (layer formed of the compound of the present invention)/electron transport layer (TPBi)/electron injection Layer (LiF)/cathode layer (Al); the substrate is glass. The current efficiency of the multilayer undoped organic electroluminescent device can reach 42.8cd/A, and the turn-on voltage is 2.6V. In the present invention, TPBi means 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene. mCP refers to 1, 3-bis (9H-carbazol-9-yl) benzene.
The apparatus used in the preparation, examples and experimental examples is described below:
NMR data and mass spectral data were obtained using a Bruker Ascend 400MHz, 700MHz NMR spectrometer (Bruker, Germany) and a Waters Xevo-G2-SQ-TOFMS mass spectrometry system (Waters, USA).
Fluorescence data were obtained by Hitachi F-7000 fluorescence spectrometer (Hitachi, Japan) and FLS-980 transient fluorescence spectrometer (Edinburgh, England). The luminance data was obtained by a PR670 spectral radiance luminance meter (taiwan pioneer technologies).
Preparation example 1 Synthesis of 4-fluoro-4' -bromobenzophenone
The reaction equation is as follows:
4-bromobenzoyl chloride (1.65g, 7.5mmol) and fluorobenzene (2.16g, 22.5mmol) were added to the reaction vessel and stirred under argon atmosphere for 10 min. Anhydrous aluminum chloride (1.50g, 11.3mmol) was slowly added in portions to the reaction vessel and stirring was continued for 1 h. The temperature is increased to 60 ℃, and the reaction is continued for 6 h. After the reaction, the reaction mixture was naturally cooled to room temperature. The reaction was quenched by slow addition of dilute hydrochloric acid and stirred until no bubbles were formed. Extracted with dichloromethane (fully dissolved upon extraction) and washed three times with water. The dichloromethane organic phase was dried thoroughly with sufficient anhydrous magnesium sulfate, filtered and concentrated. And (3) carrying out column chromatography separation on the concentrate (eluent is petroleum ether and dichloromethane in a volume ratio of 2: 1) to obtain the 4-fluoro-4' -bromobenzophenone. The structure of the product was identified as follows:
1H NMR(400MHz，CDCl3)δ7.84(dd，J＝8.6，5.5Hz，2H)，7.66(s，4H)，7.19(t，J＝8.6Hz，2H)。
13C NMR(101MHz，CDCl3)δ194.13，166.78，164.25，136.22，133.39，132.53，131.38，127.56，115.74。
preparation example 2 Synthesis of the first intermediate
The reaction equation is as follows:
9, 9-dimethylacridine (2.30g, 11mmol) was dissolved in 50mL of N, N-Dimethylformamide (DMF) and stirred at 0 ℃ under an argon atmosphere. Anhydrous potassium tert-butoxide (1.68g, 15mmol) was added in portions to the reaction and stirring was continued at 0 ℃ for 5 h. The 4-fluoro-4' -bromobenzophenone (2.79g, 10mmol) prepared in preparation example 1 was slowly added to the above reaction system, naturally warmed to room temperature, and stirred for further reaction for 12 hours. Heating to 60 ℃, continuing stirring for reaction for 12h, and cooling to room temperature. The reaction was poured into a dilute hydrochloric acid solution, washed three times with water, and then sufficiently extracted with dichloromethane. The dichloromethane organic phase was dried over sufficient anhydrous magnesium sulfate, filtered, and concentrated in vacuo to afford the crude product. The crude product was separated by column chromatography (eluent was a mixed solvent of petroleum ether and dichloromethane at a volume ratio of 5: 1) to give the first intermediate (4-bromo-4' - (9, 9-dimethylacridine) -benzophenone). The structure of the first intermediate is identified, and the result is as follows:
1H NMR(400MHz，CDCl3)δ8.04(d，J＝8.1Hz，2H)，7.78(d，J＝8.2Hz，2H)，7.69(d，J＝8.2Hz，2H)，7.53-7.44(m，4H)，7.05-6.91(m，4H)，6.33(d，J＝9.4Hz，2H)，1.69(s，6H)。
13C NMR(101MHz，CDCl3)δ194.74，145.75，140.44，136.48，136.08，132.59，131.83，131.57，130.88，130.83，127.85，126.43，125.39，121.22，114.45，36.12，31.07。
PREPARATION EXAMPLE 3 Synthesis of the second intermediate
The reaction equation is as follows:
the first intermediate obtained in preparation example 2 (0.94g, 2mmol) was reacted with potassium acetate (1.17g, 12mmol), bis-pinacolato borate (1.53g, 6mmol) and catalytic amount of [1,1' -bis (diphenylphosphino) ferrocene under argon atmosphere]Palladium dichloride [ Pd (dppf) Cl2]Added to 40mL of dry 1, 4-dioxane and reacted at 90 ℃ for 12 h. After the reaction was completed, the reaction was quenched by adding water and extracted with ethyl acetate. Drying the organic phase with anhydrous magnesium sulfate, filtering, vacuum concentrating, adding 1:10 volume ratio of acetic acidAnd (3) performing column chromatography separation by using a mixed solvent of ethyl ester and petroleum ether as an eluent to obtain a second intermediate (4-pinacol borate-4' - (9, 9-dimethylacridine) -benzophenone). The structure of the second intermediate is identified, and the result is as follows:
1H NMR(400MHz，CDCl3)δ8.13-8.06(m，2H)，8.00(d，J＝8.2Hz，2H)，7.93-7.87(m，2H)，7.60-7.44(m，4H)，7.02(dtd，J＝18.7，7.3，1.6Hz，4H)，6.37(dd，J＝8.0，1.6Hz，2H)，1.73(s，6H)，1.41(s，12H)。
13C NMR(101MHz，CDCl3)δ196.90，145.55，140.48，139.51，136.87，134.73，132.76，130.89，130.67，129.00，126.44，125.35，121.12，114.39，84.28，36.09，31.11，24.92。
EXAMPLE 1 Synthesis of the target Compound
The reaction equation is as follows:
3, 5-bis (N-phenylbenzimidazole) -1-bromobenzene (1.19g, 2.2mmol), the second intermediate obtained in preparation example 3 (1.03g, 2mmol) and a catalytic amount of Pd (PPh)3)4(69.3mg, 0.06mmol) was added to a reaction vessel, 40mL of toluene and 5mL of saturated potassium carbonate solution were added under an argon atmosphere, and the reaction was stirred at 85 ℃ for 12 h. After the reaction is finished, adding water to quench the reaction, extracting with ethyl acetate, taking an organic phase, concentrating, performing column chromatography separation on the obtained concentrate by using a mixed solvent of ethyl acetate and n-hexane with the volume ratio of 1:10 as an eluent to obtain a yellow solid, and then recrystallizing to obtain a target compound DMAC-BP-BPi. The structure of the target compound is identified, and the result is as follows:
1H NMR(400MHz，CDCl3)δ8.23(s，2H)，8.14-8.01(m，4H)，7.96(d，J＝8.3Hz，2H)，7.61(d，J＝7.4Hz，8H)，7.49(td，J＝7.6，7.1，1.9Hz，6H)，7.42(t，J＝7.4Hz，2H)，7.34(dd，J＝7.6，2.1Hz，4H)，7.28(d，J＝8.1Hz，3H)，7.05(td，J＝8.1，7.7，1.6Hz，2H)，6.98(td，J＝7.4，1.4Hz，2H)，6.37(dd，J＝8.2，1.4Hz，2H)，1.71(s，6H)。
13C NMR(101MHz，CDCl3)δ195.44，145.60，140.48，137.24，136.82，132.66，131.00，130.95，130.66，127.69，127.53，126.93，126.52，124.91，121.12，117.90，117.21，114.49，111.82，36.09，31.11。
LC-MS C60H43N5O+h calculated value 850.3546; found 850.3521.
Experimental example 1
First, the characterization data of the target compound DMAC-BP-Bpi (example 1) are shown in Table 1.
TABLE 1
Two, non-doped organic electroluminescent devices (non-doped OLEDs)
1. Single layer undoped OLEDs
The target compound DMAC-BP-Bpi (example 1) was applied in OLEDs to form an ITO anode layer (indium tin oxide layer)/hole injection layer (molybdenum trioxide, MoO)3Thickness 2 nm)/luminescent layer (DMAC-BP-BPi pure film layer, thickness 60 nm)/electron injection layer (LiF, thickness 0.5 nm)/cathode layer (Al, thickness 110nm), and the substrate is a glass device. The DMAC-BP-BPi pure film layer is the layer formed by adopting the target compound DMAC-BP-Bpi. The resulting device is a single layer undoped device that does not contain a hole transport layer and an electron transport layer. Specific methods of fabricating the device may refer to those known in the art. The single layer undoped OLEDs were subjected to performance testing, and the results are shown in table 2 below.
TABLE 2
Note: the data of comparative example 1 are "single layer undoped red fluorescent organic light emitting diode based on bipolar small molecules, zuo yunlong, etc., physico-chemical bulletin, 2010, 26 (3): 531- "of the corresponding plant, and 534".
2. Multilayered undoped OLEDs
The target compound DMAC-BP-Bpi (example 1) was applied as a light-emitting layer to multi-layered OLEDs to form an ITO anode layer (indium tin oxide layer)/hole injection layer (molybdenum trioxide MoO)3Thickness 2 nm)/hole transport layer (mCP, 45 nm)/luminescent layer (DMAC-BP-BPi pure film layer, thickness 30 nm)/electron transport layer (TPBi, 40 nm)/electron injection layer (LiF, thickness 0.5 nm)/cathode layer (Al, thickness 110nm), and the substrate is a glass device. The light-emitting layer of the device only adopts a target compound DMAC-BP-Bpi, and is not doped with other compounds. Methods for fabricating the multilayered undoped OLEDs may refer to those known in the art.
The performance tests were performed on the multilayered undoped OLEDs, and the results are shown in table 3 below.
TABLE 3
Note: the data of comparative example 2 are the effect data of the undoped multilayer light-emitting device a of CN 107721981A.
As can be seen from the table, the compound of the present invention is a highly efficient thermally-excited delayed fluorescence molecule having a bipolar transport property. The compound can be applied to single-layer undoped and multi-layer undoped organic electroluminescent devices.
As can be seen from the table, the current efficiency of the single-layer undoped device of the present invention can reach 10.1cd/A, and the turn-on voltage is 2.7V. The device of the type has the advantages of few layers, easy assembly, realization of higher device performance and important application value. In addition, the invention forms a multilayer undoped device after introducing other functional layers (a hole transport layer and an electron transport layer), the efficiency of the multilayer undoped device is further improved, the current efficiency can reach 42.8cd/A, the turn-on voltage is only 2.6V, and the application potential of the multilayer undoped device can be greatly improved.
The present invention is not limited to the above-described embodiments, and any variations, modifications, and substitutions which may occur to those skilled in the art may be made without departing from the spirit of the invention.
Claims (10)
1. A compound having the structure of formula (I):
in the formula (I), R1、R2、R3、R4、R5、R6、R7And R8Represents a substituent at an arbitrary position on a benzene ring;
R1and R2Each independently selected from hydrogen, C1-C6 alkyl or C1-C6 alkoxy;
R3、R4、R5and R6Each independently selected from hydrogen, nitro, cyano or C1-C6 alkyl; r7And R8Each independently selected from hydrogen or C1-C6 alkyl.
2. The compound of claim 1, wherein:
R1and R2Each independently selected from hydrogen, C1-C3 alkyl or C1-C3 alkoxy;
R3、R4、R5and R6Each independently selected from hydrogen, nitro, cyano or C1-C3 alkyl; r7And R8Each independently selected from hydrogen or C1-C3 alkyl.
3. A compound of claim 1, wherein R is1And R2Each independently selected from hydrogen, methyl, ethyl, methoxy or ethoxy.
4. The method of claim 3A compound characterized in that R1And R2Are all hydrogen.
5. The compound of claim 1, wherein:
R3、R4、R5and R6Each independently selected from hydrogen, nitro or cyano;
R7and R8Each independently selected from hydrogen, methyl or ethyl.
6. The compound of claim 1, wherein the compound has the structure of formula (II):
7. a process for the preparation of a compound according to any one of claims 1 to 6, comprising the steps of:
(1) reacting a compound shown in a formula (A) with a compound shown in a formula (B) to obtain a first intermediate;
in the formula (A), R7And R8Each independently selected from hydrogen or C1-C6 alkyl; x is bromine or iodine; in the formula (B), R1And R2Each independently selected from hydrogen, C1-C6 alkyl or C1-C6 alkoxy;
(2) reacting the first intermediate with a borate ester to obtain a second intermediate;
(3) reacting the second intermediate with a compound shown as a formula (C) to obtain a compound shown as a formula (I);
in the formula (C), R3、R4、R5And R6Each independently selected from hydrogen, nitro, cyano or C1-C6 alkyl; y is selected from chlorine, bromine or iodine.
8. The method of claim 7, wherein:
in the step (1), a compound shown as a formula (B) and a compound shown as a formula (A) in a molar ratio of 1.02-1.15: 1 are reacted under a first solvent and a first alkaline assistant to obtain a first intermediate;
in the step (2), reacting a first intermediate with borate in a molar ratio of 1: 1.5-4 in a second solvent, a first catalyst and a second basic auxiliary agent to obtain a second intermediate; wherein the borate is bis-pinacol borate;
in the step (3), the compound shown as the formula (C) with the molar ratio of 1.02-1.15: 1 and a second intermediate react under the conditions of a third solvent, a second catalyst and a third basic auxiliary agent to obtain the compound shown as the formula (I).
9. The method of claim 8, wherein:
in the step (1), the first solvent is N, N-dimethylformamide or N, N-dimethylacetamide, and the first alkaline auxiliary agent is potassium tert-butoxide;
in the step (2), the second solvent is 1, 4-dioxane, the first catalyst is [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride, and the second alkaline auxiliary agent is potassium acetate; the reaction temperature is 85-95 ℃, and the reaction time is 8-16 h;
in the step (3), the third solvent is toluene or ethylbenzene, and the second catalyst is tetrakis (triphenylphosphine) palladium; the third alkaline auxiliary agent is potassium carbonate; the reaction temperature is 80-90 ℃, and the reaction time is 8-16 h.
10. The use of a compound according to any one of claims 1 to 6 in the preparation of an organic electroluminescent device which is a single-layer undoped organic electroluminescent device or a multilayer undoped organic electroluminescent device;
the single-layer undoped organic electroluminescent device comprises an anode layer, a hole injection layer, a light emitting layer, an electron injection layer and a cathode layer; wherein the light-emitting layer is formed from the compound according to any one of claims 1 to 6; the current efficiency of the single-layer non-doped organic electroluminescent device is greater than 10cd/A, and the starting voltage is lower than 2.8V;
the multilayer undoped organic electroluminescent device comprises an anode layer, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode layer; wherein the light-emitting layer is formed from the compound according to any one of claims 1 to 6; the current efficiency of the multilayer undoped organic electroluminescent device is larger than 39cd/A, and the starting voltage is lower than 2.7V.
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